Graded arc for high na and immersion lithography

ABSTRACT

A method of forming a device using a graded anti-reflective coating is provided. One or more amorphous carbon layers are formed on a substrate. An anti-reflective coating (ARC) is formed on the one or more amorphous carbon layers wherein the ARC layer has an absorption coefficient that varies across the thickness of the ARC layer. An energy sensitive resist material is formed on the ARC layer. An image of a pattern is introduced into the layer of energy sensitive resist material by exposing the energy sensitive resist material to patterned radiation. The image of the pattern introduced into the layer of energy sensitive resist material is developed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 11/488,528 (Attorney Docket No. APPM/011048), filed on Jul. 18,2006, which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a graded anti-reflectivecoating, its use in integrated circuit fabrication, and a method fordepositing the graded anti-reflective coating.

2. Description of the Related Art

In recent years integrated circuits have evolved into complex devicesthat commonly include millions of transistors, capacitors, resistors,and other electronic components on a single chip. Therefore, there is aninherent demand for increased circuit densities, as well as a continualdemand for faster and more efficient circuit components. The combineddemands for faster circuits having greater circuit densities imposescorresponding demands on the materials used to fabricate such integratedcircuits. This demand for faster circuits with greater circuit densitieshas led to the use of low resistivity conductive materials, such ascopper and/or low dielectric constant insulating materials having adielectric constant less than about 3.8.

The demands for faster components having greater circuit densities alsoimposes demands on process sequences used for integrated circuitmanufacture. For example, in process sequences using conventionallithographic techniques, a layer of energy sensitive resist is generallyformed over a stack of material layers on a substrate. An image of apattern may then be introduced into the energy sensitive resist layer.Thereafter, the pattern introduced into the energy sensitive resistlayer may be transferred into one or more layers of the material stackformed on the substrate using the layer of energy sensitive resist as amask. The pattern introduced into the energy sensitive resist may thenbe transferred into a material layer(s) using a chemical and/or physicaletchant. A chemical etchant is generally designed to have a greater etchselectivity for the material layer(s) than for the energy sensitiveresist, which generally indicates that the chemical etchant will etchthe material layer(s) at a faster rate than it etches the energysensitive resist. The faster etch rate for the one or more materiallayers of the stack typically prevents the energy sensitive resistmaterial from being consumed prior to completion of the patterntransfer.

Lithographic imaging tools used in the manufacture of integratedcircuits employ deep ultraviolet (DUV) imaging wavelengths, i.e.,wavelengths of 248 nm or 193 nm, to generate resist patterns. The DUVimaging wavelengths are generally known to improve resist patternresolution as a result of the diffraction effects being reduced at theshorter wavelengths. However, the increased reflective nature of manyunderlying materials, i.e., polysilicon and metal silicides, forexample, may operate to degrade the resulting resist patterns at DUVwavelengths. Furthermore, for printing features with smaller pitches(≦250-300 nm) immersion lithography using lenses with a high numericalaperture is typically used. As the numerical aperture (NA) increasesbeyond 0.9, and pitch sizes decrease to less than 100 nm, lightreflectance from non-normal incidence angles becomes a significantsource of reflection.

One technique proposed to minimize reflections from an underlyingmaterial layer uses an anti-reflective coating (ARC). The ARC is formedover the reflective material layer prior to resist patterning. The ARCgenerally suppresses the reflections off the underlying material layerduring resist imaging, thereby providing more accurate patternreplication in the layer of energy sensitive resist. However, currentlyavailable anti-reflective coating techniques fail to account for thelight reflectance from non-normal incidence angles.

In view of conventional photolithographic techniques, there exists aneed in the art for an anti-reflective coating that reduces lightreflectance from non-normal incidence angles.

SUMMARY OF THE INVENTION

Embodiments of the invention pertain to forming a graded anti-reflectivecoating. According to one embodiment one or more amorphous carbon layersare formed on a substrate. An anti-reflective coating (ARC) is formed onthe one or more amorphous carbon layers wherein the ARC layer has anabsorption coefficient that varies across the thickness of the ARClayer. An energy sensitive resist material is formed on the ARC layer.An image of a pattern is introduced into the layer of energy sensitiveresist material by exposing the energy sensitive resist material topatterned radiation. The image of the pattern introduced into the layerof energy sensitive resist material is developed. In another embodiment,the ARC layer and the amorphous carbon layer are deposited in-situ inthe same processing system or the same processing chamber withoutbreaking vacuum.

According to another embodiment, a method of forming a device isprovided. The method comprises forming one or more amorphous carbonlayers on a substrate. An ARC layer is formed on the one or moreamorphous carbon layers wherein the ARC layer has an absorptioncoefficient that varies across the thickness of the ARC layer, whereinthe one or more amorphous carbon layers and the ARC layer are depositedin-situ in the same processing system or the same processing chamberwithout breaking vacuum.

According to another embodiment, a layer of anti-reflective coating(ARC) material for use in a photolithographic process is provided. TheARC layer is formed from a gas mixture comprising one or more carbonsources, a silicon source, and an oxygen source wherein the ARC layerhas an absorption coefficient that varies across the thickness of theARC layer. In another embodiment, the gas mixture further comprises aninert gas.

In additional embodiments, the ARC layer has an absorption coefficientin a range between about 0 and about 1.0. In another embodiment, the ARClayer is formed by modulating the flow of one or more carbon sources, aninert gas, a silicon source, and an oxygen source.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentinvention can be understood in detail, a more particular description ofthe invention, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this invention and are therefore not to beconsidered limiting of its scope, for the invention may admit to otherequally effective embodiments.

FIG. 1 illustrates a schematic of an apparatus that may be used topractice embodiments of the invention;

FIGS. 2 a-2 e illustrate schematic cross-sectional views of a substratestructure at different stages of integrated circuit fabricationincorporating one embodiment of the graded anti-reflective coating ofthe current invention;

FIGS. 3 a-3 e illustrate schematic cross-sectional views of a damascenestructure at different stages of integrated circuit fabricationincorporating one embodiment of the graded anti-reflective coating ofthe current invention;

FIGS. 4 a-4 c illustrate schematic cross-sectional views of a substratestructure at different stages of integrated circuit fabricationincorporating one embodiment of the graded anti-reflective coating ofthe current invention; and

FIGS. 5 a-5 d illustrate schematic cross-sectional views of a substratestructure at different stages of integrated circuit fabricationincorporating a multi-layer graded ARC structure.

DETAILED DESCRIPTION

Embodiments of the invention generally provide a graded anti-reflectivecoating, use of the graded anti-reflective coating in integrated circuitfabrication, and a method for depositing the graded anti-reflectivecoating. The optical properties, specifically the optical propertiesmeasured by the light absorption coefficient (k) and the index ofrefraction (n) continuously vary throughout the film.

FIG. 1 illustrates schematic representation of a wafer processing system10 that may be used to perform graded ARC and amorphous carbon layerdeposition. This apparatus generally includes a process chamber 100, agas panel 130, a control unit 110, and other hardware components, suchas power supplies, vacuum pumps, etc. that are known in the art to beused to manufacture integrated circuit components. Examples of thesystem 10 may include CENTURA® systems, PRECISION 5000®, systems andPRODUCER™ systems, all of which are commercially available from AppliedMaterials Inc., of Santa Clara, Calif.

The process chamber 100 generally includes a support pedestal 150, whichis used to support a substrate, such as a semiconductor wafer 190. Thispedestal 150 may typically be moved in a vertical direction inside thechamber 100 using a displacement mechanism 160. Depending on thespecific process, the wafer 190 may be heated to a desired temperatureby an embedded heating element 170 within pedestal 150. For example, thepedestal 150 may be resistively heated by applying an electric currentfrom an AC supply 106 to the heating element 170, which then heats thewafer 190. A temperature sensor 172, such as a thermocouple, forexample, may be embedded in the wafer support pedestal 150 in order tomonitor the temperature of the pedestal 150 through cooperativeinteraction with a process control system (not shown). The temperatureread by the thermocouple may be used in a feedback loop to control thepower supply 106 for the heating element 170 such that the wafertemperature can be maintained or controlled at a desired temperaturethat is suitable for the particular process application. Alternatively,the pedestal 150 may utilize alternative heating and/or coolingconfigurations known in the art, such as, plasma and/or radiant heatingconfigurations or cooling channels (not shown).

A vacuum pump 102 may be used to evacuate the process chamber 100 and tomaintain the desired gas flows and dynamic pressures inside the chamber100. A showerhead 120, through which process gases may be introducedinto the chamber 100, may be located above the wafer support pedestal150. The showerhead 120 may generally be connected to a gas panel 130,which controls and supplies various gases used in different steps of theprocess sequence.

The showerhead 120 and wafer support pedestal 150 may also form a pairof spaced electrodes. Therefore, when an electric field is generatedbetween these electrodes, the process gases introduced into the chamber100 by the showerhead 120 may be ignited into a plasma, assuming thatthe potential between the spaced electrodes is sufficient to initiateand maintain the plasma. Typically, the driving electric field for theplasma is generated by connecting the wafer support pedestal 150 to asource of radio frequency (RF) power 104 through a matching network (notshown). Alternatively, the RF power source and matching network may becoupled to the showerhead 120, or coupled to both the showerhead 120 andthe wafer support pedestal 150.

Plasma enhanced chemical vapor deposition (PECVD) techniques generallypromote excitation and/or disassociation of the reactant gases by theapplication of the electric field to a reaction zone near the substratesurface, creating a plasma of reactive species immediately above thesubstrate surface. The reactivity of the species in the plasma reducesthe energy required for a chemical reaction to take place, in effectlowering the required temperature for such PECVD processes.

In embodiments of the invention, amorphous carbon layer deposition isaccomplished through plasma enhanced thermal decomposition of ahydrocarbon compound, such as propylene (C₃H₆) for example. Propylenemay be introduced into the process chamber 100 under the control of thegas panel 130. The hydrocarbon compound may be introduced into theprocess chamber as a gas with a regulated flow through the showerhead120, for example.

Proper control and regulation of the gas flows through the gas panel 130may be conducted by one or more mass flow controllers (not shown) and acontrol unit 110 such as a computer. The showerhead 120 allows processgases from the gas panel 130 to be uniformly distributed and introducedinto the process chamber 100 proximate the surface of the wafer.Illustratively, the control unit 110 may include a central processingunit (CPU) 112, support circuitry 114, and various memory unitscontaining associated control software 116 and/or process related data.Control unit 110 may be responsible for automated control over varioussteps required for wafer processing, such as wafer transport, gas flowcontrol, temperature control, chamber evacuation, and other processesknown in the art to be controlled by an electronic controller.Bi-directional communications between the control unit 110 and thevarious components of the apparatus 10 may be handled through numeroussignal cables collectively referred to as signal buses 118, some ofwhich are illustrated in FIG. 1.

The heated pedestal 150 used in the present invention may bemanufactured from aluminum, and may include a heating element 170embedded at a distance below the wafer support surface 192 of thepedestal 150. The heating element 170 may be manufactured from anickel-chromium wire encapsulated in an Incoloy sheath tube. By properlyadjusting the current supplied to the heating element 170, the wafer 190and the pedestal 150 may be maintained at a relatively constanttemperature during wafer preparation and film deposition processes. Thismay be accomplished through a feedback control loop, in which thetemperature of the pedestal 150 is continuously monitored by thetemperature sensor 172 embedded in the pedestal 150. This informationmay be transmitted to the control unit 110 via a signal bus 118, whichmay respond by sending the necessary signals to the heater power supply.Adjustment may subsequently be made in the power supply 106 so as tomaintain and control the pedestal 150 at a desirable temperature, i.e.,a temperature that is appropriate for the specific process application.Therefore, when the process gas mixture exits the showerhead 120 abovethe wafer 190, plasma enhanced thermal decomposition of the hydrocarboncompound occurs at the surface 191 of the heated wafer 190, resulting ina deposition of an amorphous carbon layer on the wafer 190.

In one embodiment of the invention the graded ARC layer can be formed bya plasma CVD reaction of a carbon source, a silicon source, and anoxygen source. In some embodiments an inert gas such as helium or argonis also added to stabilize the plasma and control the deposition rate.In one specific embodiment a graded ARC layer is formed by forming aplasma and varying the composition of a gaseous mixture comprisingmethylsilane, carbon dioxide, and helium. Such a deposition processbeneficially incorporates oxygen into the film, which also helps varythe light absorption coefficient of the graded ARC layer.

The graded ARC material according to the present invention can bedeposited to have, at deep UV radiation wavelengths, a varyingrefractive index (n) of between about 1 and about 2.2 inclusive. In somespecific embodiments the light absorption coefficient (k) can be variedsignificantly (e.g. between about 0 and 1.0) over a narrow refractiveindex range of between 1 and 2.2 inclusive.

The as-deposited graded ARC layer generally has an adjustable oxygen,carbon, and hydrogen content. Controlling the oxygen, carbon, andhydrogen content of the graded ARC layer is desirable for tuning itsoptical properties. For example, as the oxygen content increases thelight absorption coefficient decreases.

The light absorption coefficient of the graded ARC layer may be variedbetween about 0 to about 1.0 at wavelengths below about 250 nm, makingit suitable for use as an anti-reflective coating (ARC) at DUVwavelengths. The absorption coefficient of the graded ARC layer may bevaried as a function of the deposition temperature.

The absorption coefficient of the graded DARC layer may also be variedas a function of the additive used in the gas mixture. In particular,the presence of H₂ in the gas mixture can increase the k value by about10% to about 100%. The absorption coefficient may also be modified byvarying power. For example, the k value will increase as powerdecreases. Another way to modify the k value is to modify the flow rateof gases. For example, increasing the flow of silane or other Si—Hcontaining molecule will increase the k value.

Integrated Circuit Fabrication Processes

A. Graded ARC with Amorphous Carbon Hardmask

FIGS. 2 a-e illustrate schematic cross-sectional views of a substrate200 at different stages of an integrated circuit fabrication sequenceincorporating a graded DARC layer with an amorphous carbon layer as ahardmask. In general, the substrate 200 refers to any workpiece on whichprocessing is performed, and a substrate structure 250 is used togenerally denote the substrate 200 together with other material layersformed on the substrate 200. The substrate 200 may be part of a largerstructure (not shown), such as a STI (shallow trench isolation)structure, a gate device for a transistor, a DRAM device, or a dualdamascene structure as in the current example. Depending on the specificstage of processing, the substrate 200 may correspond to a siliconsubstrate, or other material layer that has been formed on thesubstrate. FIG. 2 a, for example, illustrates a cross-sectional view ofa substrate structure 250, having a material layer 202 that has beenconventionally formed thereon. The material layer 202 may be an oxide(e.g., SiO₂). In general, the substrate 200 may include a layer ofsilicon, silicides, metals, or other materials. FIG. 2 a illustrates oneembodiment in which the substrate 200 is silicon having a silicondioxide layer formed thereon.

FIG. 2 b illustrates an amorphous carbon layer 204 deposited on thesubstrate structure 250 of FIG. 2 a. The amorphous carbon layer 204 isformed from a gas mixture of a hydrocarbon compound and an inert gassuch as Argon (Ar) or helium (He). The hydrocarbon compound has ageneral formula C_(x)H_(y) where x has a range of between 2 and 10 and yhas a range of between 2 and 22. For example, propylene (C₃H₆), propyne(C₃H₄), propane (C₃H₈), butane (C₄H₁₀), butylene (C₄H₈), butadiene(C₄H₆), acetelyne (C₂H₂), pentane, pentene, pentadiene, cyclopentane,cyclopentadiene, benzene, toluene, alpha terpinene, phenol, cymene,norbornadiene, as well as combinations thereof, may be used as thehydrocarbon compound. Liquid precursors may be used to deposit amorphouscarbon films. The use of liquid precursors in the deposition ofamorphous carbon films is further discussed in United States PatentApplication Publication No. 2005/0287771, published Dec. 29, 2005,entitled LIQUID PRECURSORS FOR THE CVD DEPOSITION OF AMORPHOUS CARBONFILMS, which is herein incorporated by reference to the extent it doesnot conflict with the current specification. These liquid precursorsinclude but are not limited to toluene, alpha terpinene (A-TRP), andnorbornadiene (BCHD). Similarly, a variety of gases such as hydrogen(H₂), nitrogen (N₂), ammonia (NH₃), or combinations thereof, amongothers, may be added to the gas mixture, if desired. Argon (Ar), helium(He), and nitrogen (N₂) may be used to control the density anddeposition rate of the amorphous carbon layer. The addition of H₂ and/orNH₃ can be used to control the hydrogen ratio of the amorphous carbonlayer.

In general, the following deposition process parameters may be used toform the amorphous carbon layer. The process parameters range from awafer temperature of about 100° C. to about 500° C., a chamber pressureof about 1 torr to about 20 torr, a hydrocarbon gas (C_(x)H_(y)) flowrate of about 50 sccm to about 50,000 sccm (per 8 inch wafer—forexample), a RF power of between about 3 W/in² to about 20 W/in², and aplate spacing of between about 200 mils to about 1,200 mils. The aboveprocess parameters provide a typical deposition rate for the amorphouscarbon layer in the range of about 100 Å/min to about 10,000 Å/min andmay be implemented on a 300 mm substrate in a deposition chamberavailable from Applied Materials, Inc. of Santa Clara, Calif. Thethickness of the amorphous carbon layer is variable, depending on thespecific stage of processing. Typically, the amorphous carbon layer mayhave a thickness in the range of about 500 Å to about 10,000 Å.

Further aspects of one embodiment of the amorphous carbon layer 204 aredescribed in commonly assigned U.S. Pat. No. 6,573,030, issued Jun. 3,2003, entitled METHOD FOR DEPOSITING AN AMORPHOUS CARBON LAYER, which isincorporated herein by reference to the extent it does not conflict withthe current specification.

The graded ARC layer 206 may be formed on the amorphous carbon layer204. The graded ARC layer 206 suppresses the reflections of theunderlying layers providing accurate pattern replication of the layer ofenergy sensitive resist. The graded ARC layer 206 may be conventionallyformed on the amorphous carbon layer 204 using a variety of CVDprocesses such as PECVD. In one embodiment, the graded ARC layer 206 isformed by forming a plasma from a gaseous mixture of a carbon source, asilicon source, an oxygen source, and an inert gas. The silicon sourcemay include silane, disilane, chlorosilane, dichlorosilane,trimethylsilane, and tetramethylsilane. The silicon source may alsoinclude an organosilicon compounds such as tetraethoxysilane (TEOS),triethoxyfluorosilane (TEFS), 1,3,5,7-tetramethylcyclotetrasiloxane(TMCTS), dimethyldiethoxy silane (DMDE), octomethylcyclotetrasiloxane(OMCTS), and combinations thereof. The oxygen source may include oxygen(O₂), ozone (O₃), nitrous oxide (N₂O), carbon monoxide (CO), carbondioxide (CO₂), water (H₂O), 2,3-butanedione, or combinations thereof.The inert gas is selected from a group comprising argon, helium, neon,krypton, xenon, and combinations thereof. The carbon sources areselected from a group comprising propylene (C₃H₆), propyne (C₃H₄),propane (C₃H₈), butane (C₄H₆), butylene (C₄H₈), butadiene (C₄H₆),acetelyne (C₂H₂), pentane, pentene, pentadiene, cyclopentane,cyclopentadiene, benzene, toluene, alpha terpinene, phenol, cymene,norbornadiene, as well as combinations thereof. In one embodiment, thegaseous mixture comprises silane (flow rate of 10-2000 sccm), carbondioxide (flow rate of 100-100000 sccm), and helium flow rate of 0-10000sccm). The varying optical properties of the ARC layer are achieved byvarying the flow rates of the aforementioned gases.

In one embodiment, the amorphous carbon and graded ARC layer are formedin-situ in the same system or process chamber without breaking vacuum.This in-situ layer functions not only as an anti-reflective coating butalso functions as a hardmask. The in-situ layer is deposited under thesame conditions as the amorphous carbon layer but a silicon source suchas silicon, silicon carbide, trimethylsilane, or silane is addedfollowed by an oxygen precursor. Flow modulation of the gases in thechamber allows for graded deposition of the in-situ layer.

A layer of energy sensitive resist material 208 may be formed on thegraded ARC layer 206. The layer of energy sensitive resist material 208may be spin coated on the substrate to a thickness within the range ofabout 2000 Å to about 6000 Å. Most energy sensitive resist materials aresensitive to ultraviolet (UV) radiation having a wavelength less thanabout 450 nm. DUV resist materials are generally sensitive to UVradiation having wavelengths of 245 nm or 193 nm. In one embodiment, anadhesion promoter, such as hexamethyldisilazane (HMDS), which serves tobond the energy sensitive resist material to the ARC layer, is usedbetween the graded ARC layer 206 and the energy sensitive resistmaterial 208.

An image of a pattern may be introduced into the layer of energysensitive resist material 208 by exposing such energy sensitive resistmaterial 208 to UV radiation via mask 210. The image of the patternintroduced in the layer of energy sensitive resist material 208, may bedeveloped in an appropriate developer to define the pattern through suchlayer, as shown in FIG. 2 c. Thereafter, referring to FIG. 2 d, thepattern defined in the energy sensitive resist material 208 istransferred through both the graded ARC layer 206 and the amorphouscarbon layer 204. The pattern is transferred through both the graded ARClayer 206 and the amorphous carbon layer 204 using the energy sensitiveresist material 208 as a mask. The pattern is transferred through thegraded ARC layer 206 using a gas mixture comprising ahydrogen-containing fluorocarbon (C_(x)F_(y)H_(z)) and one or more gasesselected from the group consisting of hydrogen (H₂), nitrogen (N₂),oxygen (O₂), argon (Ar), and helium (He). The amorphous carbon layer 204can be etched using ozone, oxygen, or ammonia plasmas alone or incombination with hydrogen bromide (HBr), nitrogen (N₂), carbontetrafluoride (CF₄), argon (Ar), and others. Both layers can be etchedin-situ with different process steps. In-situ should be broadlyconstrued and includes, but is not limited to, in a given chamber, suchas in a plasma chamber, or in a system, such as an integrated clustertool arrangement, without exposing the material to interveningcontamination environments, such as breaking vacuum between processsteps or chambers within a tool. An in-situ process typically minimizesprocess time and possible contaminants compared to relocating thesubstrate to other processing chambers or areas.

FIG. 2 e illustrates the completion of the integrated circuitfabrication sequence by the transfer of the pattern defined in theamorphous carbon layer 204 through the silicon dioxide layer 202 usingthe amorphous carbon layer 204 as a hardmask. After the silicon dioxidelayer 202 is patterned, the amorphous carbon layer 204 may be strippedfrom the substrate 200 by etching it in an ozone, oxygen, ammonia plasmaalone or in combination with fluorinated compounds, nitrogen, orhydrogen plasmas.

In a specific example of a fabrication sequence, the pattern defined inthe graded ARC layer and the amorphous carbon hardmask may beincorporated into the structure of the integrated circuit, such as adamascene structure. Damascene structures are typically used to formmetal interconnects on integrated circuits. Other structures include aSTI (shallow trench isolation) structure, a gate device for atransistor, a DRAM device, or a dual damascene structure.

FIGS. 3 a-3 e illustrate schematic cross-sectional views of a substrate260 at different stages of a damascene structure fabrication sequenceincorporating an amorphous carbon layer therein. Depending on thespecific stage of processing, substrate 260 may correspond to a siliconsubstrate, or other material layer that has been formed on thesubstrate. FIG. 3 a, for example, illustrates a cross-sectional view ofa substrate 260 having a dielectric layer 262 formed thereon. Thedielectric layer 262 may be an oxide (e.g., silicon dioxide,fluorosilicate glass). In general, the substrate 260 may include a layerof silicon, silicides, metals, or other materials known in the art asdielectric layers. Other embodiments contemplate the use ofnon-dielectric materials, such as, conductive or semiconductivematerials.

FIG. 3 a illustrates an embodiment of the invention in which thesubstrate 260 is silicon having a fluorosilicate glass layer formedthereon. The dielectric layer 262 has a thickness of about 5,000 Å toabout 10,000 Å, depending on the size of the structure to be fabricated.A graded ARC layer 264 is formed on the dielectric layer according tothe process parameters discussed above. In one embodiment graded ARClayer and an amorphous carbon layer are formed in-situ, represented byin-situ layer 264. The in-situ layer 264 functions both as ananti-reflective coating and as a hardmask. The in-situ layer 264 isdeposited under the same conditions as the amorphous carbon layer but asilicon source such as silicon, silicon carbide, TMS, or silane is addedfollowed by an oxygen precursor. Flow modulation of the gases in thechamber allows for graded deposition of the in-situ layer 264. Theamorphous carbon portion of in-situ layer 264 has a thickness of about500 Å to about 1 μm and the graded ARC portion of in-situ layer 264 canbe between about 200 Å to about 2000 Å. Referring to FIG. 3 b, thein-situ layer 264 may be patterned and etched to define contact/viaopenings 266 and to expose the dielectric layer 262, in areas where thecontacts/vias are to be formed. The in-situ layer 264 may be patternedusing conventional lithography techniques and etched using oxygen and/orammonia plasmas. The pattern may be transferred through the graded ARCportion of in-situ layer 264 using a gas mixture comprising ahydrogen-containing fluorocarbon (C_(x)F_(y)H_(z)) and one or more gasesselected from the group consisting of hydrogen (H₂), nitrogen (N₂),oxygen (O₂), argon (Ar), and helium (He). The amorphous carbon layerportion of in-situ layer 264 may be etched using ozone, oxygen, orammonia plasmas alone or in combination with hydrogen bromide (HBr),nitrogen (N₂), carbon tetrafluoride (CF₄), argon (Ar), and others. Bothlayers can be etched in-situ with different process steps.

The contact/via openings 266 formed in the in-situ layer 264 may betransferred into the dielectric layer 262 using the amorphous carbonportion of the in-situ layer 264 as a hard mask as shown in FIG. 3 c.The contacts/vias 266 are etched using reactive ion etching or otheranisotropic etching techniques. After the contacts/vias 266 aretransferred into the dielectric layer 262, the remaining in-situ layer264 may be stripped from dielectric layer 262 using the etchantsdiscussed above, as illustrated in FIG. 3 d.

Referring to FIG. 3 e, a metallization structure may be formed in thecontacts/vias 266 using a conductive material 274 such as aluminum,copper, tungsten, or combinations thereof. Typically, copper is used toform the metallization structure due to its low resistivity (about 1.7μΩ-cm). The conductive material 274 may be deposited using chemicalvapor deposition, physical vapor deposition, electroplating, orcombinations thereof, to form the damascene structure. Preferably, abarrier layer 272 such as tantalum, tantalum nitride, or other suitablebarrier is first deposited conformally in the metallization structure inorder to prevent metal migration into the surrounding dielectricmaterial layer 262. Additionally, the dielectric layer 262 preferablyhas a low dielectric constant (dielectric constants less than about 4.5)so as to prevent capacitive coupling between adjacent contacts/vias 266of the metallization structure.

B. Graded Anti-Reflective Coating (ARC)

FIGS. 4 a-4-c illustrate schematic cross-sectional views of a substrate300 at different stages of an integrated circuit fabrication sequenceincorporating a graded anti-reflective coating (ARC). In general, thesubstrate 300 refers to any workpiece on which film processing isperformed, and a substrate structure 350 may be used to generally denotethe substrate 300 together with other material layers formed on thesubstrate 300. Depending on the specific stage of processing, substrate300 may correspond to a silicon substrate, or other material layer,which has been formed on the substrate. FIG. 4 a, for example,illustrates a cross-sectional view of a substrate structure 350 in whichthe substrate 300 is an oxide layer formed on a silicon wafer.

A graded ARC layer 302 may be formed on substrate 300 according to theprocess parameters described above. The graded ARC layer may have arefractive index (n) in the range of about 1.0 to 2.2 and an absorptioncoefficient (k) in the range of about 0 to about 1.0 at wavelengths lessthan about 250 nm, thus making it suitable for use as an ARC at DUVwavelengths. The graded ARC layer includes an absorption coefficient (k)that varies across the thickness of the layer. That is, the graded ARClayer has an absorption coefficient gradient formed therein. Such agradient is formed as a function of the temperature and the compositionof the gas mixture during layer formation. When the graded ARC has agradient, it is possible for the refractive indices (n) and theabsorption coefficients (k) of the two material layers to be similar sothere is minimal reflection and maximum transmission into the gradedARC. Then the refractive index (n) and absorption coefficient (k) of theamorphous carbon ARC may be gradually adjusted to absorb all of thelight transmitted therein. In this embodiment, the n and k values of thebottom of the graded ARC layer are similar to the n & k values of thesubstrate. In one embodiment, the absorption coefficients (k) of the twomaterial layers match within a range between about +/−0.05.

The thickness of the graded ARC layer may also be varied depending onthe specific stage of processing. Typically, the graded ARC layer has athickness of about 200 Å to about 2000 Å.

FIG. 4 b depicts a layer of energy sensitive resist material 304 formedon the substrate structure 350 of FIG. 4 a. The layer of energysensitive resist material can be spin coated on the substrate to athickness within the range of about 2000 Å to about 6000 Å. The energysensitive resist material may be selected as a material that issensitive to DUV radiation having a wavelength less than 250 nm. In thisembodiment, the n & k values at the top of the graded ARC layercorrespond to the n & k values of the energy sensitive resist.

An image of a pattern may be introduced into the layer of energysensitive resist material 304 by exposing such energy sensitive resistmaterial 304 to DUV radiation via mask 306. The image of the patternintroduced into the layer of energy sensitive resist material 304 may bedeveloped in an appropriate developer to define the pattern through suchlayer. Thereafter, as shown in FIG. 4 c, the pattern defined in theenergy sensitive resist material 304 may be transferred through thegraded ARC layer 302. The pattern may be transferred through the gradedARC layer 302 using the energy sensitive resist material 304 as a mask.The pattern may be transferred through the graded ARC layer 302 byetching it using a gas mixture comprising a hydrogen-containingfluorocarbon (C_(x)F_(y)H_(z)) and one or more gases selected from thegroup consisting of hydrogen (H₂), nitrogen (N₂), oxygen (O₂), argon(Ar), and helium (He). After the graded ARC layer 302 is patterned, suchpattern may be optionally transferred into the substrate 300.

C. Multi-Layer Graded Anti-Reflective Coating (ARC)

FIGS. 5 a-5 d illustrate schematic cross-sectional views of a substrate400 at different stages of an integrated circuit fabrication sequenceincorporating a multi-layer graded anti-reflective coating (ARC)structure. In general, the substrate 400 refers to any workpiece onwhich film processing is performed and a substrate structure 450 is usedto generally denote the substrate 400 together with other materiallayers formed on the substrate 400. Depending on the specific stage ofprocessing, substrate 400 may correspond to a silicon substrate, orother material layer, which has been formed on the substrate. FIG. 5 a,for example, illustrates a cross-sectional view of a substrate structure450 in which the substrate 400 is a silicon wafer.

A first graded ARC layer 402 may be formed on the substrate 400according to the process parameters described above. The first gradedARC layer 402 may be designed primarily for light absorption, and assuch, the first graded ARC layer 402 may have an index of refraction inthe range of about 1.0 and about 2.2 and an absorption coefficient (k)in the range of about 0.0 to about 1.0 at wavelengths less than about250 nm. The thickness of the first graded ARC layer 402 may be variabledepending on the specific stage of processing. Typically, the firstgraded ARC layer 402 has a thickness in the range of about 300 Å toabout 1500 Å.

A second graded ARC layer 404 may be formed on the first graded ARClayer 402. The second graded ARC layer 404 may also be formed accordingto the process parameters described above. The second graded ARC layer404 may also have an index of refraction in the range of about 1.0 andabout 2.2 and an absorption coefficient (k) in the range of about 0.0 toabout 1.0 at wavelengths less than about 250 nm. Additional graded ARClayers may be included in the multi-layered graded ARC structure.

FIG. 5 b illustrates a layer of energy sensitive resist material 406formed on the substrate structure 450 of FIG. 5 a. The layer of energysensitive resist material may be spin coated on the substrate to athickness within the range of about 2000 Å to about 6000 Å. The energysensitive resist material is sensitive to DUV radiation having awavelength less than 250 nm. An image of a pattern may be introducedinto the layer of energy sensitive resist material 406 by exposing suchenergy sensitive resist material 406 to DUV radiation via mask 408. Theimage of the pattern introduced into the layer of energy sensitiveresist material 406 may be developed in an appropriate developer todefine the pattern through such layer as shown in FIG. 5 c. Thereafter,referring to FIG. 5 d, the pattern defined in the energy sensitiveresist material 406 may be transferred through both graded ARC layers404, 402 using the energy sensitive resist material 406 as a mask. Thepattern may be transferred through the graded ARC layers 404, 402 byetching them using an appropriate chemical etchant such as a gas mixturecomprising a hydrogen-containing fluorocarbon (C_(x)F_(y)H_(z)) and oneor more gases selected from the group consisting of hydrogen (H₂),nitrogen (N₂), oxygen (O₂), argon (Ar), and helium (He). After themulti-layer ARC is patterned, such pattern is optionally transferredinto the substrate.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

1. A method of forming a device, comprising: forming one or moreamorphous carbon layers on a substrate; forming an anti-reflectivecoating layer on the one or more amorphous carbon layers, wherein theanti-reflective coating layer has an absorption coefficient that variesacross the thickness of the anti-reflective coating layer, and theforming the anti-reflective coating layer comprises reacting at least anorganosilicon compound in a plasma; forming an energy sensitive resistmaterial on the anti-reflective coating layer; introducing an image of apattern into the energy sensitive resist material by exposing the energysensitive resist material to patterned radiation; and developing theimage of the pattern introduced into the energy sensitive resistmaterial.
 2. The method of claim 1, further comprising: transferring thepattern to the anti-reflective coating layer using the energy sensitiveresist material as a mask; transferring the pattern through the one ormore amorphous carbon layers; and transferring the pattern defined inthe at least one region of the one or more amorphous carbon layers intothe substrate using the one or more amorphous carbon layers as a mask.3. The method of claim 1, wherein the one or more amorphous carbonlayers and the anti-reflective coating layer are deposited in-situ inthe same processing system or the same processing chamber withoutbreaking vacuum.
 4. The method of claim 1, wherein the anti-reflectivecoating layer has an varied index of refraction that is in a rangebetween about 1.0 to about 2.2.
 5. The method of claim 1, wherein theabsorption coefficient of the bottom of the anti-reflective coatinglayer corresponds to the absorption coefficient of the amorphous carbonlayer within a range of +/−0.05.
 6. The method of claim 1, wherein theabsorption coefficient of the top of the anti-reflective coating layercorresponds to the absorption coefficient of the energy sensitive resistwithin a range of +/−0.05.
 7. The method of claim 1, wherein theorganosilicon compound comprises an oxygen-containing organosiliconcompound.
 8. The method of claim 1, wherein the organosilicon compoundcomprises tetraethoxysilane (TEOS), triethoxyfluorosilane (TEFS),1,3,5,7-tetramethylcyclotetrasiloxane (TMCTS), dimethyldiethoxy silane(DMDE), octomethylcyclotetrasiloxane (OMCTS), or combinations thereof.9. The method of claim 1, wherein forming the anti-reflective coatinglayer further comprises reacting an oxygen source and an inert gas inthe plasma to form a silicon-containing, oxygen-containing, andcarbon-containing anti-reflective coating layer.
 10. The method of claim1, wherein the anti-reflective coating layer has a first refractiveindex (n) and first absorption coefficient (k) similar to the refractiveindex (n) and absorption coefficient (k) of the one or more amorphouscarbon layers and has a second refractive index (n) and a secondabsorption coefficient (k) similar to the refractive index (n) andabsorption coefficient (k) of the energy sensitive resist material. 11.The method of claim 1, wherein a refractive index at the bottom of theanti-reflective coating layer substantially matches a refractive indexof the one or more amorphous carbon layers.
 12. The method of claim 1,wherein a refractive index of the energy sensitive resist materialsubstantially matches a refractive index of a top surface of theanti-reflective coating layer.
 13. The method of claim 1, wherein theanti-reflective coating layer has a thickness between about 200 Å andabout 2000 Å.
 14. A layer of anti-reflective coating material for use ina photolithographic process, the anti-reflective coating layer formedfrom a gas mixture of at least an organosilicon compound, wherein theanti-reflective coating layer has a refractive index and an absorptioncoefficient that are gradually adjusted across the thickness of theanti-reflective coating layer.
 15. The anti-reflective coating layer ofclaim 14, wherein the refractive index of the anti-reflective coatinglayer is varied in the range of 1.0 to 2.2.
 16. The anti-reflectivecoating layer of claim 14, wherein the organosilicon compound comprisesan oxygen-containing organosilicon compound.
 17. The anti-reflectivecoating layer of claim 14, wherein the gas mixture further comprises atleast an oxygen source, a carbon source, an inert gas or combinationsthereof, and the carbon source in the gas mixture has the generalformula C_(x)H_(y), wherein x has a range of 2 to 10, and y has a rangeof 2 to
 22. 18. The anti-reflective coating layer of claim 14, whereinthe anti-reflective coating layer has an absorption coefficient gradienttherein with a first refractive index (n) and a first absorptioncoefficient (k) similar to the refractive index (n) and absorptioncoefficient (k) of an amorphous carbon material deposited thereunder anda second refractive index (n) and a second absorption coefficient (k)similar to the refractive index (n) and absorption coefficient (k) of anenergy sensitive resist material deposited thereon.
 19. Theanti-reflective coating layer of claim 14, wherein the refractive indexat the bottom of the anti-reflective coating layer substantially matchesa refractive index of an amorphous carbon material deposited thereunder.20. The anti-reflective coating layer of claim 14, wherein a refractiveindex of an energy sensitive resist material deposited thereonsubstantially matches the refractive index of a top surface ofanti-reflective coating layer.